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CHAPTER - 00
REACTION MECHANISM

ISOMERISM IN ORGANIC COMPOUNDS

Compounds having same molecular formula but different physical and chemical properties are called
isomers an the phenomenon is known as isomerism.

STRUCTURAL ISOMERISM
Compounds having same molecular formula, but different structures are called structural isomers
Chain isomerism
This type of isomerism is arise due to the difference in the arrangement of carbon chains
* Chain isomerism in alkanes
1. Butane (2 isomers)

1 2 2 1 1 2 1
CH3 CH2 CH2 CH3 CH 3 CH CH 3
n - B utane
1 CH 3
2 types of hydrogen atom s
Isobutane
( 2 types of m ono halogenation products)
2 types of hydrogen atoms
( 2 types of monohalogenation products)

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2. Pentane (3 isomers)

1 2 3 1 2 3 4
2 1
CH3 CH2 CH2 CH2 CH3 CH3 CH CH2 CH3

n-pentane 1CH3
3-types of hydrogen atoms Iso pentane
(3-types of monohalogenation products) 4-types of hydrogen atoms
(4-types of monohalogenation products)

1
CH3
1
1
CH3 C CH3

1CH3

Neopentane
1-types of hydrogen atom
(Only one mono-halogenation product)

3. Hexane (5 isomers)
4. Heptane (9 isomers)
5. Octane (18 isomers)
6. Nonane (35 isomers)
7. Decane (75 isomers)
* Chain isomerism in alcohols

CH 3 CH 2 CH 2 CH 2 OH & CH3 CH CH2 OH

n- butanol
CH3
Isobutanol
* Chain isomerism in alkenes

CH3 CH2 CH CH2 & CH3 C CH2

n butene
CH3
Isobutene

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Position isomerism
This type of isomerism is arise due to the difference in the positions of functional groups, substituents
or, unsaturation in the carbon chain.

a) CH3 CH2 CH2 OH & CH3 CH OH

CH3

b) CH3 CH2 CH2 Cl & CH3 CH CH3

Cl

c) CH3 CH2 CH CH2 & CH3 CH CH CH2

Cl Cl
Cl

Cl
d)
Cl
Cl
o-dichloro benzene m-dichloro benzene
p-dichloro benzene

Functional isomerism
Compounds having same molecular formula but different functional groups are called Functional
isomers.
i) Alcohol and ether
CH3 CH2 OH & CH3 O CH3 C2H6O
ii) Carboxylic acids and esters

CH3 CH2 C OH CH3 C O CH3 C3H6O2 

&

O O
iii) Aldehydes , Ketones, Unsaturated alcohols and Unsaturated ethers

CH3 CH2 CH3 C CH3 , CH2 CH CH2 OH ,

C H,

O O

& CH2 CH OCH3 C3H6 O

vi) Dienes, Allenes and Alkynes
CH2 CH CH CH2, CH2 C CH CH3 & CH3 C C CH3 C4H6 
(Diene) (Allene) Alkyne
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Note:
Number of double bond equivalents possible for an organic compound

 n  V  2 
  1 n: Number of atoms of a particular element
 2 
v: Valency of the corresponding atom
2 double bonds are equivalent to one triple bond. One double bond is equivalent to one cyclic compound.
1. Number of double bond equivalents possible for C4H6

4  4  2 6 1  2
C 4 H6   1
2 2

 4  3 1  2
2. Number of double bond equivalents for C3H6O

3  4  2  6 1  2  1  2  2 
C 3H6O    1
2 2 2

 3  3  0 1  1
v) Aromatic alcohol, phenols and ethers

CH2OH OH O CH3

, CH3 & C7H8O

vi) Primary secondary and tertiary amines

CH3
CH3 CH2 CH2 NH2 , CH3 CH2 NH CH3 & CH3 N CH3 C3H9N
primary
Secondary
Tertiary

vii) Amides and oximes

CH 3 CH 2 C NH 2 & CH3 CH2 CH N OH C3H7NO

O

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viii) Nitro alkanes and alkylnitrites

CH3 NO2 & CH3 O N O

Nitromethane
Methylnitrite
ix) Cyanides (nitriles) and isocyanides (Carbilamine /Isonitrile)
CH3 C N & CH3 N C
Tautomerism
This is a special type of functional isomerism in which isomers exist in a dynamic equilibrium.
It arises due to the migration of a hydrogen atom from one poly valent atom to the other within the
same molecule with necessary rearrangements for linkages.
1) Keto-enol tautomerism

H O O H

CH2 C H CH2 C H

Keto form Enol form

( 99.99%) (Negligible)

H O O H

CH2 C CH3 CH2 C CH3

 
(99.7%) (0.3%)

O OH
H
 H

(98.8%) (1.2%)

In all the three monocarbonyl compounds listed above, the greater percentage of ketoform is due
to the greater strength of C O  bond (364 kJmol-1) as compared to C=C  bond (254 kJmol-1).

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Note: Hydrogen bonding and resonance increases the percentage of enol form

H
O O
O O
C  C
CH3 C CH3 C C
CH3 CH3
H H C

Acetylacetone H
(24%)
(76%)

H
O O
O O

C  C C C
C CH3
CH3 C
H H
H
(11%)
(89%)

H
O O
O O
C C
C  C
C C
H H
H
(4%) (96%)

OH
O
H

H

0.1% 99.9% (Aromatic)

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2) Nitro-acinitro tautomerism

H O H
O
CH3 CH3 CH N
CH N
 O
O
Acinitroform
Nitroform
3.Nitroso oximino tautomerism

CH3 CH N O CH3 CH N OH

Oximinoform
Nitrosoform
Note:
Oximes are functional isomers of amides and they are tautomers of nitroso compounds.

4) Imine -Enamine tautomerism C NH Imine

CH3 CH CH NH CH3 CH CH NH2


enamine form
Imine form
5) Amido - Imidol tautomerism

H O O H

HN C NH 2 HN C NH 2

Amido form Imidol form

6) Thioamido - Imithiol tautomerism

H S SH

HN C NH2 HN C NH2


Thioamido form Imithiol form

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Conditions for tautomerism
1. Presence of atleast one   hydrogen
2. Presence of electronegative elements such as O, N, S,.... with multiple bonds [=C=O, -N=O, =C=S,
-C  N, =C=NH .....]

R O
R C C H

R

O No tautomerisation due to the absence of  hydrogenatom

C 


Note: Tautomerism is not observed in parabenzoquinone because H-atoms are present on double
bonded carbon atoms of the ring.
O
H H

H H
O

P-benzoquinone
Note:
In addition to 1,3- migration, 1, 5 and 1,7-migrations are also observed in tautomerisation.
1
2 O O
H H
3
O
C O5 C
4
H
1
O H O
2

4
5
C C
6 H O H
H O7

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METAMERISM

This type of isomerism is arise due to the unequal distribution of carbon atoms on the either side of the
functional group.
Eg: CH3CH2OCH2CH3 &CH3OCH2CH2CH3

Note: Metamerism is not observed in the molecule CH3 CH2 O CH3

Example for some functional groups showing metamerism are O , NH ,
O

C O , S ,etc

O O

Note: CH3 CH2 C O CH3 and CH3 C O CH2 CH3 are considered as
metamers.
Ring Chain Isomerism
1. Alkenes and cycloalkanes

CH3 CH CH2 and (C3H6)

2. Alkynes and cycloalkenes

CH3 C CH and (C3H4)

3. Unsaturated alcohols and cyclic ethers

O
CH2 CH CH2 OH and (C3H6O)

OH
O
Note: Other two cyclic isomers possible for the formula (C3H6O) are CH3 and

Hybridisation of different types of carbon

1.Carbon with 4-  bonds  sp3 hybridisation (No unhybridised ‘p’ orbitals are present)
2. Carbon with 1   bond  sp2 hybridisation (One unhybridised ‘p’ orbital is present)
3. Carbon with 2   bonds  sp hybridisation (Two unhybridised ‘p’ orbitals are present)
Note:
• Normal sp3 bond angle  109028' (Total 6 tetrahedral angles are present around an sp3 hybridised ‘C’)
• Normal sp2 bond angle  1200 (Total 3-1200 angles are present around an sp2 hybridised ‘C’)
• Normal sp bond angle  1800 (2-1800 angles)

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An sp hybridised carbon and carbons bonded to it are linearly arranged.

0 0
180 180
H H
H C C C C H
H sp sp
H

linear

Methods for electron transfer in a covalent bond

1. Resonance
When the actual structure of a molecule is represented by the help of more than one electronic
arrangement, the molecule said to have resonance.i.e.,delocalisation of  electrons occurs during
resonance.
eg: Resonance in benzene
i) Kekule structures

Cannonical structures Resonance hybrid

ii) Dewar structures

Each Kekule structure give around 39% and each Dewar structures give around 7% to the total
resonance hybrid of benzene.
Note:

n!

Total number of resonance structures possible for a benzoid aromatic compound
  
n ! n 1 !
2 2

where ‘n’ is the number of  electrons involved in resonance

6!
Eg: Number of resonance structures possible for benzene  5
3! 4!

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Evidences for resonance in benzene
1. Difference in the expected bond length
0
C-C single bond length = 1.54 A
0
C=C double bond length = 1.34 A
0 0
 We can expect three 1.54 A length bonds and three 1.34 A length bonds in benzene. But in
0
 
benzene all the carbon-carbon bond lengths are identical 1.39 A 
 

2. Benzene doesn’t gives addition reaction under normal condition because the double bonds in benzene
are stabilized by resonance
3. Calculation of resonance energy in benzene

i) + H2 H  28.6 k cal mol 1

ii) + 2 H2 H  2  28.6 k cal mol 1

+ 3H2
iii) H expected = 3×-28.6

= -85.8 k cal mol-1

-1
H observed = -49.8 K cal mol
 Resonance energy in benzene = 85.8-49.8 = 36 K cal mol-1

 Each double bonds in benzene are stabilised by around 12 K cal mol-1

Resonance in different types of systems
1. Resonance involving   bonds

CH2 CH CH CH2 CH2 CH CH CH2

2. Resonance involving +ve charge

CH 2 CH CH 2 CH 2 CH CH 2

3. Resonance involving -ve charge

CH2 CH CH2 CH2 CH CH2

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4. Resonance involving lone pair

CH2 CH NH2 CH2 CH NH2

5. Resonance involving free radical

CH 2 CH CH 2 CH 2 CH CH 2

 In the all five cases represented above, resonance involves    conjugation

Resonance effect or Mesomeric effect (R/M - effect)
Polarity produced in a molecule by the interaction between  bonds or between  bond and lone
pair of electrons (or non bonding electrons) of an adjacent atom is known as resonance effect or
mesomeric effect. There are two types +R or +M and –R or -M.

CH2 CH CH CH2 CH2 CH CH CH2

+R/+M Effect
If the group attached to an unsaturated or conjugated system is electron releasing through
resonance., the effects called as +R effect.

CH2 CH NH2 CH2 CH NH2

Examples for some groups showing +R effect : NH2, NHR, NR2, OH , OR , X

-R/-M Effect
If the group attached to an unsaturated or conjugated system is electron withdrawing through
resonance, the effect is called as -R effect.

O O-
+
CH2 CH N CH2 CH N
-
O-
O

Examples for some groups showing ‘-R’ effect NO2, CN , SO3H , COOH , CHO etc.
Applications

1. Aromatic amines are less basic as compared to aliphatic amines, because due to resonance, the
lone pair of electrons on nitrogen is delocalised over the aromatic ring and it is therefore less easily
available for protonation.

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NH2

2. Amides are less basic as compared to amines because due to resonance, the lone pair on N in
amides are delocalized over the carbonyl group.

R C NH2

3. Phenols are more acidic as compared to alcohol because the phenoxide ion is stabilized by
resonance.

OH O-
- +
H

Hyperconjugation (Baker-Nathan effect)

It involves the migration of a C-H  -electrons of an alkyl group directly attached to an atom of an
unsaturated system or to an atom with an unshared ‘p’ orbital (free radicles or carbocations)
1. Hyperconjugation in carbocation

H
H H H
H

C CH2 H C CH2 H+ C CH2 H C CH2
H H H H+

+
H
C H
H C
H

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2. Hyper conjugation in unsaturated system

H H
H C CH CH2 H C CH CH2 2 more structures

H H

C H
H H C C
H H

3. Hyper conjugation in free radicals

H H

CH2 H C CH2 2 more structures

H C

H H

C H
H H C
H

 In all the three cases represented above, hyperconjugation involves   

conjugation. Since there is a carbon-hydrogen bond absent in all the hyperconjugative structures,
hyperconjugation is also known as no -bond resonance.
The necessary condition for hyperconjugation is the presence of atleast one  
hydrogen atom. As the number of   hydrogen atom in an alkyl group increases, its hyper conjugative
effect also increases. Therefore hyper conjugative effect of some alkyl group follows the order.

H R R
H

H C .> R C >H C . > R C

H H R R
(3  hydrogen) (2- hydrogen) (1-hydrogen) (no  -hydrogen)

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Applications
1. Alkyl groups are ortho -para directing groups for electrophiles on aromatic ring due to hyperconjugation

H

H C H

2. Shortening of C-C single bond length adjacent to multiple bonds.

H H+

H CH H C CH CH2
3
C CH 3 2 1
2 1

H H

Due to hyperconjugation C2-C3 bond in propene have a partial double bond character.
3. Relative stabilities of alkene
As the number of   hydrogen atoms possible for an alkene increases, the number of
hyperconjugative structures and stability increases

CH3

CH2  CH2  CH3  CH  CH2  CH3  CH  CH  CH3  CH3 C CH CH3 < CH3 C C CH3
no  hydrogen 3  hydrogen 6 hydrogen
CH3 CH3
9- hydrogen
12- hydrogen

INDUCTIVE EFFECT (I EFFECT)

The polarisation produced in a  bond due to the polarisation of an adjacent  bond is called
inductive effect.
-I Effect
If the group attached to the end of a carbon chain is electron withdrawing through inductive effect,
the effect is called as -I effect.

     
CH3 CH2 CH2 CH2 Cl

-I effect of some groups follows the order NR3 > NO2 > CN > SO3H > CHO >
COOH > F> Cl > Br > I

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+I Effect
If the group attached to the end of a carbon chain is electron releasing through inductive effect, the
effect is called as +I effect.

    
CH3 CH2 CH2 CH2 O

R R
 
The +I effect of some groups follows the order O  COO  R C > H C >

R R

H H

R C >H C

H H

Applications
1. Acidity of carboxylic acid
The carboxylate anion generated from carboxylic acid after the removal of a proton is stabilized by
resonance. This is responsible for the acidity of carboxylic acids.

O O-
O
H+
C C
C
O H O- O

Presence of electron withdrawing groups on carbonyl carbon increases the stability of carboxylate
anion and therefore such groups increases the acidity of carboxylic acid. On the other hand electron
releasing group on carbonyl carbon decreases the stability of carboxylate anion and therefore such
groups decreases the acidity of carboxylic acid.
a) Effect of electron withdrawing substituents (halogens)
• Presence of electron withdrawing halogens increases the acidity of carboxylic acids through -I effect.

O O

CH 3 C OH F CH 2 C OH

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• The acidity of carboxylic acids increases with increase in number of halogen atom

CH2F C OH CHF2 COOH CF3 COOH

• As the distance of halogen from the carbonyl group increases, the acidity of haloacids decreases.

O F O

F CH2 CH2 C OH CH3 CH C OH

   

• The electronegativity of halogen decreases from F  I  The acidity of   halo acids decreases
from F  I

CH3 CH C OH CH3 CH C OH

Cl O F O
b) Effect of electron releasing substituents (Alkyl groups)
Electron releasing alkyl groups decreases the acidity of carboxylic acids through +I effect

O
O
CH 3 C OH H C OH

Basicity of amines
Presence of electron releasing groups on nitrogen increases its electron density through their +I effect
and therefore such groups increases the basicity of amines.

CH 3 NH 2 < CH 3 CH2 NH2

On the other hand electron with drawing groups decreases the basicity of amines through - I effect

CH3 NH2 > CF3 NH2

ELECTROMERIC EFFECT (E - EFFECT)
It involves the complete transfer of a  bond to the one of the bonded atom in presence of an
attacking reagent

C=C 
reagent added
 C C
reagent removed

Since the effect operates only in the presence of an attacking reagent, it is a temporary effect

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+E effect
If the electrons of the   bond are transferred to that atom of the   bond to which the reagent get
finally attached is called +E effect

CH2=CH2+ H+ CH2 CH3

- E effect
If the electrons of the  bond are transferred to that atom of the  -bond other than the one to which
the reagent get finally attached is called -E effect.

C=O NC C O
CN +

REACTION INTERMEDIATES
1. Carbocations (carbonium ions) : They are intermediate species carrying a positive charge on carbon
Classification

R CH2 R CH R C+
CH3

R R

Methyl carbocation (1o) (2o) (3o)

Structure
In carbocation, carbon is in sp2 hybridised state. The three half filled sp2 hybridised orbitals form three
'  ' bonds. The unhybridised ‘p’ orbital is unoccupied.

1 1 1 C
sp 2

 The carbon in carbocations are associated with 6 electrons in its valence shell
stability
Stability in terms of inductive effect
Electron releasing alkyl groups decreases the magnitude of +ve charge on carbocation through +1
effect and there fore such groups increases their stability.

 stability of carbocations follows the order 3° > 2° > 1° > CH3

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R
CH3 < R CH2 <R CH R <R C R

On the other hand electron withdrawing group increases the magnitude of +ve charge on the carbon
by - I effect and there for such groups decreases their stability

CH3 CH2 > CF3 CH2

NOTE :
As the ‘S’ character or electronegativity of carbon bearing the +ve charge increases the stability of
carbocation decreases

CH3  CH2  CH2  CH  CH  C

Stability in terms of hyper conjugation
As the number of  - hydrogen possible for a carbocation increases the number of hyper conjugative
structures and therefore stability increases

CH3

CH3  CH3  CH2  CH3  CH  CH3  CH3 C CH3

no  hydrogen 3 hydrogen 6 hydrogen

9 hydrogen

Stability in terms of resonance

a) Resonance stabilisation of allylic carbocation

CH2 CH CH2 CH CH CH2

b) Resonance stabilisation of benzylic carbocation

CH 2 CH 2

3 more structures

The magnitude of +ve charge is located at ortho- para positions. There fore electron releasing
groups at ortho-para positions increases the stability of benzylic carbocation and electron withdrawing
groups at ortho-para positions decreases their stability.

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CH2 CH2 CH2

> >

OCH3 NO2

As the number of phenyl groups possible for the benzylic carbo cation increases, its resonance
stabilisation is also increases.

C6H5 CH2 < C6H 5 CH+ C6H5 < C6H5 C+ C6H5

C6H5
If the positively charged carbon is bonded to a hetero atom carrying lone pair of electrons, the carbocation
is stabilised by resonance.

CH 3 O CH 2 CH 2 < CH 3 CH 2 O CH 2

CF 3 CH2 < C F

R C O R C O
Acylium cation More stable resonace structure
(Octect all atoms are completed)

NOTE :
Cycloheptatrienyl cation (Tropylium cation) is more stable than  C6H5 3 C

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Reason
The carbocation is the resonance hybrid of 7 identical structures and also the cation is aromatic in
nature.
The so far discovered most stable carbocation is

Reason:-

C
. The bent orbitals in cyclopropyl ring release electrons to be vacant ‘p’-

orbital of carbocation (  - conjugation)

Rearrangement of carbocation
Less stable primary and secondary carbocations rearrange to more stable 3° or 2° carbocations
through 1, 2 shifts.

CH3

CH3 1,2- methyl shift

C CH2 CH3 C CH2 CH3

CH3 CH3
(10) (30)

H
1,2-hydride shift
CH3 C CH2 CH3 C CH3
CH3 CH3
(10) (30)

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RING EXPANSIONS DURING REARRANGEMENT OF CARBOCATIONS

CH3

CH3
(less stable)
CH3 0
3
CH3
CH3
CH3
CH3
CH3

0
3 (more stable)

2. Carbanion
They are intermediate species carrying a negative charge on carbon.
Classification

R C R
CH3 R
R CH2 CH R
(Methyl R
0 0
Primary (1 ) Secondary (2 )
carbanion) Tertiary (30 )

Structure

In carbanions, carbon is in sp3 hybridised state. The three half filled sp3 hybridised orbitals form 3 
bonds. 4th sp3 hybridised orbital contains a pair of electrons. But in resonance stabilised carbanions
like, allyl, benzyl etc the negatively charged carbon is sp2 hybridised.

sp 3
Carbanion (Pyramidal)

 The carbon in carbanion are associated with 8 electrons in its valence shell.

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NOTE:
Methyl carbanion and ammonia (NH3) are iso structural and iso electronic.

C N
H H H H
H H

(10 electrons) (10 electrons)

Stability
Stability in terms of inductive effect.
Electron releasing group increases the magnitude of -ve charges on carbanion through +I effect
and such groups decreases their stability.  The stability of carbanion is in the order..
CH3 > 10 > 20> 30

CH3 > R CH2 > R2 CH > R3 C

On the otherhand electron withdrawing group decreases the magnitude of carbanion through -I
effect and such groups increases their stability.

CH3 CH2 < C F3 CH2

Stability in terms of resonance

a) Resonance stabilisation of allylic carbanion

CH2 CH CH2 CH2 CH CH2

b) Resonance stabilisation of benzylic carbanion

CH 2 CH 2

3 more structures

The magnitude of -ve charge is located at ortho-para positions. Therefore electron withdrawing
groups at ortho-para positions increase the stability of benzylic carbanion and electron releasing group
at ortho- para positions decreases their stability.

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CH2 CH2 CH2

< <

NO2
OCH3

3. Free radicals
They are neutral electron deficient chemical species carrying an unpaired electron. They are generated
as a result of homolytic bond cleavage.

Cl Cl 2Cl
Classification

CH3 R CH2 R CH R R C R

Methyl freeradical 10 20 30
Structure
In free radicals carbon is in sp2 hybridisation. The three half filled sp2 hybridised orbitals form 3 
bonds. The unshared electron is present in the unhybridised ‘p’ orbital.

sp 2 Planar geometry

 The carbon in free radicals are associated with 7e- in their valence shell.
Stability
Stability in terms of hyperconjugation
As the number of   hydrogen atom possible for a free radical increase, the number of hyperconjugative
structures and therefore stability increases. Therefore the stability increases in the order 30 > 20> 10>
CH3

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CH3
  
CH 3  CH3  C H2  CH3  C H  CH3 < CH3 C CH3
No  hydrogen 3 hydrogen 6 hydrogen

9-hydrogen

Stability in terms of resonance

a) Resonance stabilisation of allylic free radical.

CH 2 CH CH 2 CH 2 C CH 2

b) Resonance stabilization of benzylic free radical.

CH2 CH2

3 more structures

As the number of phenylic group possible for a benzylic free radical increases the resonance
stabilisation is also increases.

C6H5 CH2 < (C6H5)2 CH < (C6H5)3C

4. Carbenes
They are neutral, electron deficient chemical species carrying two unshared electrons on carbon.
Eg: CH2 - Methylene, CCl2 - Dichlorocarbene
Carbenes are the reaction intermediates in the following reactions
A. Carbyl amine reaction

R NH2 + CHCl3 +3 KOH R NC +3 KCl +3 H2O

B. Riemer-Tiemann reaction

OH OH
CHO
KOH
+ CHCl3

Salicylaldehyde

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Both Riemer-Tiemann reaction and carbylamine reaction involves a dichloro carbene intermediate.

Cl Cl Cl
-
-
H2O
C - Cl-
OH + H C Cl Cl C
Cl Cl
Cl
Structure
A carbene is known to exist in two states. If the two unshared electrons goes to two different orbitals
(parallel spin) the carbene is in triplet state.
• In triplet state of carbene the carbon is in ‘sp’ hybridised state
• The two half filled ‘sp’ hybridized orbitals form 2 bonds
• The two unshared electrons are present in two different unhybridised ‘p’ orbitals.
• There is a net magnetic moment in this state

Triplet state 

sp

If the two unshared electrons goes to a single orbital (antiparallel state) the carbene is in singlet
state.
• In this form of carbon is in sp2 hybridised state
• The two half filled sp2 hybridised orbitals form of 2  bonds
• The two unshared electrons are present in the third sp2 hybridised orbital
• The unhybridised ‘p’ orbital is unoccupied

Singlet state  C

2
sp
Stability
The ground state of carbene is considered to be the triplet state, because for the formation of
singlet state electron must be paired. It requires some extra energy to overcome the electron-electron
repulsion

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NOTE:
If the carbon in carbene is bonded to two groups, each containing a lone pair, the carbene is
stabilised by resonance.

H2N H2N
H2N
C C C
H2N H2N H2N

5. Nitrenes
They are the nitrogen analogous of carbenes

R N R N

Singlet Triplet
Nitrenes are the reaction intermediates in Hoffmann’s bromamide reaction
O

R C NH2 + Br2 + 4 KOH R NH2 + K2CO3 + 2 KBr + 2 H2O

The reaction involves an acylnitrene intermediate and is rearranges to an alkyl isocyanate

R C N R N C O

Alkylisocyanate
Acylnitrene
(Unstable)

ELECTROPHILES AND NUCLEOPHILES

Electrophiles are electron loving chemical species (electron deficient)

Eg: R , H , NO2 , NO , X , ..... (+ve ions)

R, CH2, R N, BF3 , AlCl3, FeBr3 , SO3.... (Neutral)

Nucleophiles are nucleus loving chemical species (electron rich)

Eg: OH , NH2 , CN , R , X  , ..... (-ve ion)

H 2O , R OH , NH3, R NH2,..... (Neutral)

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Different types of organic reactions
1. Substitution reaction
a. Electrophilic substitution reaction (S.E. reaction)
The substitution reaction is carried out by an electrophile
Eg: - Electrophilic substitution reaction in benzene


H
+ E+  

Mechanism

i) Reagent E

H
slow E
ii) + E

H
E
- H+
iii) E

The second step is the slowest step and it is therefore the rate determining step
Application
• Benzene and hexadeuteriobenzene gives a particular electrophilic substitution reaction exactly at the
same rate, because cleavage of proton is not involved in rate determine step
1. Nitration

NO2

HNO3/H2SO4

Mechanism

OH -

i) 2 H 2SO 4 + HNO 3 NO 2 + 2 HSO 4 + H 3O

(Base)

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NO2

H+
ii) + NO2

2. Sulphonation

SO3H
Conc. H 2SO 4

Mechanism:

i) 2 H2SO4 SO3 + HSO4 + H3O +

SO3H
O H
O Slow
ii) + SO3 + S O S
O
O O

Friedel craft’s reaction

AlCl3
+ RCl

Mechanism:

i) R Cl + AlCl3 R + AlCl4

ii) H+
+R

Application:-
Benzene with chlorobenzene doesn’t give friedel craft’s reaction because the phenyl carbocation is
highly unstable.

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Cl

AlCl3
+ No reaction

Cl

+ AlCl3 + AlCl4

Unstable

Halogenation

Br

FeBr3
+ Br2 + HBr

Mechanism:

i) Br2  FeBr3  Br   FeBr4

Br


H
ii) + Br   

Ring activating groups for electrophilic substitution

Electron releasing groups increases the electron density on benzene ring and therefore such groups
activate the benzene ring for electrophilic substitution.

Eg: NH2, NHR, OH , OR ..... (+R effect)

Alkyl groups (+I and hyperconjugation)

Ring activating effect of NH2 group

NH2 NH2 NH2 NH2 NH2

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 Brilliant STUDY CENTRE LONG TERM - (IIT/AIIMS)-Chemistry
The magnitude of -ve charge is located at ortho-para positions.  Ring activating group are ortho-
para directing groups or electrophiles

NH2 NH2 NH2

E
H+
+ E +

E
(major)

Ring deactivating groups for electrophilic substitution

Electron withdrawing groups decreases the electron density on benzene ring and therefore such
groups deactivates benzene ring towards electrophilic substitution.
Eg:- NO2, -CN, -SO3H, -CHO, -COOH .... (-I and -R effect)
Halogens (-I effect)
Ring deactivating effect of cyanide group

C N C N C N C N C N

The magnitude of +ve chargee is located at ortho-para positions .  Ring deactivating groups are
meta directing groups for electrophiles

C N C N

H+
+ E
E
Anomalous behavior of halogens
Halogens are ring deactivating groups through their strong -I effect. But orthopara directing groups
for electrophiles through their weak +R effect.  Halogens are ortho-para directing deactivators. i.e.,
th reactivity of the ring is controlled by strong -I effect of halogen and orientation of the electrophile is
controlled by its weak +R effect.

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Cl

b. Nucleophilic substitution reaction

The substitution reaction carried out by nucleophile.

aq.KOH
R OH

Eg:- R X

KCN
R CN

Some steriochemical aspects

1. Optical activity
The ability of a compound to rotate the plane of vibration of plane polarised light is called optical activity.

d 
Towards right  Dextro rotatory     
 

d 
Towards left  Laevo rotatory     
 
2. Chirality
The objects that gives non-superimpossable mirror images are called chairal object and phenomenon
is known as chairality.Chirality of the molecule is the necessary condition for optical activity
3. Asymmetric carbon
In 1874 Vant-Hoff and Le-Bell pointed out that the 4- valancies of a carbon are directed towards the
corners of a regular tetrahedron.If the valancies are satisfied by 4-different groups or atoms, the molecule
become chiral and is therefore optically active. Such type of a carbon is called an asymmetric carbon.

C*
S Q
R

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4. Enantiomers
They are the optical isomers of the same compound and rotate the plane vibration of plane polarised
light equally but through opposite directions. They are nonsuper impossible mirror images of each
other

P P
C C
Q S
R S Q
R

5. Racemic mixture
An equimolar mixture of enantiomers are called racemic mixture. Optical activity of racemic mixture
are zero due to external compensation
6. Racemisation
The process of conversion of an optically active isomer into its racemic modification is called
racemisation
7. Configuration
The spacial arrangement of different, groups or atoms around a central carbon is called configuration.
In a chemical reaction, if the configuration of different bonds around the central carbon is preserved, it
is called retention of configuration. In a chemical reaction if the configuration of different bonds around
the central carbon is not preserved, it is called inversion configuration.

a a a
Y Y
Y C b b C X b C Y
H
H H
(Inversion) (Retention)

Mechanism of nucleophilic substitution reaction

SN1 mechanism (substitution nucleophilic unimolecular mechanism)

CH3 CH3

Consider the reaction CH3 C x +OH CH3 C OH + x . The SN1 mechanism

CH3 CH3
for this reaction can be explained as

CH3 CH3

1) CH3 C x 
slow
 
 CH3 C +x

CH3 CH3

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CH 3 CH 3

2) CH 3 C fast
+ OH   CH 3 C OH

CH 3 CH 3

The first step is the slowest step and it is therefore the rate determining step. This step involves only
a single reactant molecule. Therefore the mechanism is called as unimolecular.
The rate of SN1 reaction depends upon the stability of the intermediate carbocation formed in the 1st
step. Stability of carbo cation follows the order 3o  2o  1o  CH3 .  The reactivity of various alkylhalide
towards SN1 reaction follows the order 3o  2o  1o  CH3 x
Note:
Alylic and benzylic carbocations are resonance stabilised. Therefore allylic and benzylic halides
easily reacts through SN1 reaction even through they are primary halides

CH 2 =C H CH2 X X CH 2 = CH CH2

CH2 X
CH2

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Steriochemistry in SN1 reaction

Nu

C
N R R''
Nu
C R'
x R
R" C R" Retention Racemisation
R
R' R' R'
Nu R R''
C

Nu
invension

 SN1 reaction at an optically active centre gives a partial racemisation with slight excess of inversion
product (The attack of nucleophile through the side of leaving group is partially hindered by leaving X-
ions from this position)
Effect of solvents on SN1 reaction
The rate determining step of SN1 reaction involves the formation of two ions (R+ and x–) polar solvents
easily solvate these two ions. So rates SN1 reactions are greater in polar solvents. Polarprotic solvents
such as alcohol, water etc. are even more effective solvents for SN1 reaction because the x- ions
forms hydrogen bonds with the hydrogen of the OH group and R+ ions co-ordinate with the oxygen of
the OH group using its non bonding electron.

H2 O HOH
H2O
OH 2 HOH HOH
H2 O R OH2 HOH X HOH
H2O OH 2 HOH HOH
OH2
HOH

SN2 Mechanism (Substitution nucleophilic bimolecular mechanism)

SN2 reaction involves only a single step in which the nucleophile attack from the backside of the
leaving group and as a result we get a 100% inversion product and is called Walden inversion

H H H H
Nu +H C 

X  X
 Nu C X Nu C H
H

H H
(Transition state)

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The single step (rate determining step) involves two reactant species. There for the mechanism is
known as bimolecular.
Bulky groups sterically retards the backside attack of the nucleophile. As a result, SN2 reaction in
various alkylhalides follows the order

CH3  X  1O  2O  3O

Note:
Allylic and benzylic halides are also highly reactive towards SN2 reaction, because the  electrons
in allylic and benzylic group helps the cleavage of C–X bonds.
SN2 reaction at an optically active centre gives a single sterio isomer and its direction of optical
activity is unpredictable (may be dextro or laevo)
Effect of solvents on SN2 reaction
The rate determining step of SN2 reaction involves the nucleophite also. In polar prototic solvents the
nucleophile forms, H-bonds with the solvent molecules.

HOH
HOH
HOH
HOH Nu HOH

HOH HOH
HOH

 The nucleophile in a cage of H-bonds and therefore it have less nucleophilicity.  SN2 reactions are
slow in polar protic solvents. The commonly used solvents for SN2 reactions are polar aprotic solvents
such as

CH3
D.M.SO S O
Dimethyl sulphoxide CH3

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O
CH3
D.M.F H C N
Dimethyl formamide
CH3

O
CH3
D.M.A CH3 C N
Dimethyl acetamide CH3

CH3
Acetone  C O
CH3
C H 3
C = N

SN1 Vs SN2 A c e t o n i t r i t e

SN1 SN2
Nucleophilic strength unimportant Nucleophiles with high nucleophilicity
 3o>2o>1o>CH3-x  CH3x>1o>2o>3o
Polar protic solvents Weakly polar (aprotic)solvents
Rate=K[R–X] Rate =K[R–X] [Nu–]
Rearrangements are possible Rearrangement is not possible
SNi Mechanism (Internal nucleophilic substitution)
In SN1 mechanism both retention and invension of configurations are present, in SN2 mechanism
inversion configuration takes place only. There is a 3rd possibility in which complete retention of
configuration occurs (SNi mechanism)
The action of alcohols with thionyl chloride is a typical example for this reaction.

R  OH  SOCl2  R  Cl  SO2  HCl

Mechanism

O O
slow
R O S Cl R O S
i) Cl + HCl
H Cl Alkylchlorosulphite

O O

R O S Cl R O S Cl
ii)
Intimate ion pair

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iii) Intimate ion pair gives internal nucleophilic substitution

R+ O S Cl R Cl + SO2

The geometry of the intimate ion pair force the Cl– ions to attack from the same side in which the R-
O bond is originally located. There fore we get a 100% retention product
Note:
If the reaction takes place in pyridene medium, (Darzenes process), protonation of pyridene takes
place

+HCl
Cl
N
N

 The medium contains good concentration of Cl– ions. These Cl– ions gives SN 2 reaction on
alkylchlorosulphite and produce the corresponding inversion product.

Cl + R O S  RCl  SO2

Cl

Free radical Substitution Reaction

Substitution reaction is carried out by a free radical
hv
Eg: CH4  Cl2  CH3Cl  CH2Cl2  CHCl3  CCl4

Mechanism


h
i) Cl  2 Cl
Cl  Initiation
 

ii)C l  CH4   C H3  HCl 
  
Propagation
iii)C H3  Cl2  CH3Cl  C l 

 

iv) C H3  C l  CH3Cl 
   Termination
v)C H3  C H3  CH3  CH3 

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Cl

h
CH3 CH2 CH3+ Cl2  CH3 CH CH3 + CH3 CH2 Cl
(Major)
Mechanism:
Cl
CH3 CH CH3 Cl
CH3 CH CH3
o
2 ( More Stable) (Major)
CH3 CH2 CH3 Cl
CH3 CH2 CH2

The reactivity of various hydrogen atom towards free radical substitution reaction depends up on
the stability of the intermediate free radical generated.The stability of free radical follows the order
3o>2o>1o.  The reactivity of various hydrogen atoms towards free radical substitution reaction follows
the order 3o>2o>1o:
CH3 CH3

CH3 CH CH3 + Cl2 CH3 CH CH2 Cl

(Major)

Different type of H-atoms Primary Secondary Tertiary

Reactivity of corresponding H-atoms 1 3.8 5

Total no.of corresponding H-atoms 9 0 1

Total possibility of corresponding products 9 0 5

9 5
% yield of correspondig products  100 0  100
14 14

Note
Allylic and benzylic free radicals are resonance stabilised. There fore reactivity of allylic and benzylic
hydrogen towards free radical substitution reaction are greater than that of 3o H.

CH2=CH2 CH3+Cl HCl CH2

CH2=CH

CH3 CH2

Cl

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Addition Reaction
1. Electrophilic addition reaction
The addition reaction is initiated by an electrophile

Eg: CH2 CH2 + HX CH3 CH2 X

Mechanism:

i) HX H+ + X-

ii) CH2 CH2 + H+ CH2 CH3

iii) CH3 CH2 + X- CH3 CH2 X

Application:

CH3 CH CH2+ HBr CH3 CH2 CH2 Br + CH3 CH CH3

Br
(Major) (Markovnikov's rule)

Mechanism:

Br-
CH3 CH CH3 CH3 CHBr CH3
+ 0
CH3 CH CH2 + H 2 (stable more) Major

CH3 CH2 CH2

10

Note:
The addition of HBr (not other HX) to an unsymmetrical alkene in presence of a peroxide takes
place against Markonikov’s rule and is called the anti-Markovnikov’s addition or peroxide effect or
Kharasch effect.

Peroxide
CH3 CH CH2 +HBr CH3 CH2 CH2 Br

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Mechanism:

O O O
h
i) C6H5 C O O C C6H5 2 C6H5 C O

ii) C6H5 C O C6H5 + CO2

iii) C6H5 + HBr C6H6 + Br

HBr
CH3 CH CH2 Br CH3 CH2 CH2 Br
0 Br
iv) CH3 CH CH2 +Br 2 (more stable) (Major)

CH3 CH CH2
CH3 CH CH2
Br

Note: Presence of electron withdrawing groups on unsaturated carbon gives anti- markonikov’s addition

CF3 CH CH2 + HCl CF3 CH2 CH2Cl

Mechanism:

CF 3 Cl-
CH 2 CH 2 CF 3 CH 2 CH 2 Cl

CF3 CH CH 2 + H (Major)

CF 3 CH CH 3
(Unstable)

Nucleophilic addition reaction

The addition reaction is initiated by a nucleophile

O OH

R C H HCN R C H (Cyano hydrin)

CN

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Mechanism:

1) HCN H+ + CN-

R R R

H
2)
CN + C O NC C O  NC C OH
H
H H

Note:
Presence of electron withdrawing groups on carbonyl carbon increases the rates of nucleophilic addition
reaction.

CF3
CN C O


H

Free radical addition reaction

The addition reaction is initiated by a free radical

Peroxide
Eg:- CH3 CH CH2 + HBr CH3 CH2 CH2 Br
ELIMINATION REACTION
This type of reaction involves the loss of 2 atoms or groups, occurs from the same or adjacent atoms
leading to the formation of a multiple bond or its any equivalent.
  Elimination reaction;
The loss of two atoms or groups occurs from the same atom

Cl Cl Cl
-
H2O
eg: OH + H C Cl C Cl Cl-
C
Cl Cl
Cl

  Elimination reaction:
The loss of two atoms or groups occurs from two adjacent atoms.
1. Dehydration of alcohols

conc.H2SO4
CH3 CH CH2 - CH3 CH CH2
H2O
OH H

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 Brilliant STUDY CENTRE LONG TERM - (IIT/AIIMS)-Chemistry
Mechanism

H
CH 3 H2O
CH3 CH CH 2 + H + CH OH 2 CH3 CH CH2
CH 3
OH

CH 3 CH CH 2

2. Dehydrohalogenation reaction

alc.KOH
CH3 CH CH2 CH3 CH CH2
-HCl
Cl H

The reaction involves alkoxide ion (R–O–) as the reagent . R–O– is bulkier nucleophile and a strong
base. Therefore it prefer to attack the  hydrogen and produce the corresponding elimination product.
Saytzseff’s Rule
In a dehydrohalogenation reaction, the more substituted alkene will be the major product

 
CH3 alco.KOH
CH CH CH2 CH CH CH3 + CH3 CH2
CH3 CH CH2
-
HCl
H Cl H Major
(Saytzeff's rule)

Reason: More substituted alkenes have a more number of  hydrogen atoms and it is therefore stabilised
by hyperconjugation.
Exceptions for Saytzseff’s elimination
1. Dehydrofluorination reaction (Hoffmann’s elimination)

F
alc. KOH
CH3  CH  CH 2  CH3  CH 2  CH  CH 2  CH 3
 HF

Reason
The C – F bond strength is greater than C – H bond strength

 The more acidic   H (less sterically crowded   H ) will be eliminated in first step.

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2. Bredt’s rule
Bridgehead carbon has pyramidal geometry. In order to maintain pyramidal geometry, its hybridisation
should be sp3. Double bonds on bridgehead carbon makes the hybridisation sp2 (planar). Therefore
double bonds are not formed through bridgehead carbon.

Cl
alc. KOH
HCl

NOTE
Nucleophilic substitutions (both SN1 and SN2) are also difficult on bridgehead carbon.
3. Bulkier bases prefer to attack less sterically crowded   H and produce corresponding Hoff-man
elimination.

CH3

CH3 C O
CH3 CH3
CH3
CH CH CH3 CH3 CH CH CH2
CH3
  (or Bu3N )
Br

4. Bulkness around a particular   H directs the incoming base to another   H which is less sterically
crowded and produce corresponding Hoffmann’s elimination product.

CH3 Br CH3
alc. KOH CH3 C CH2 CH CH2
CH3 C CH2 CH CH3
 
CH3 CH3

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Mechanism of  -elimination reactions

1. E1 Mechanism (elimination unimolecular mechanism)

CH3 CH3

i. CH3 C 
Slow
CH3  
 CH3 C + X–

X CH3

CH 3 CH3

ii. CH 3 C + Nu CH3 C

CH 2 H CH2

Since the rate determining step of E1 reaction involves the formation of a carbocation intermediate,
the E1 reactivity order of various alkyl halides follows the sequence 30 > 20 > 10
2. E2 mechanism (elimination biomolecular mechanism)

X X
 NuH
CH2 CH2 CH2 CH2 
 X
 CH2=CH2

H H

Nu T.S
Nu

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Bulkness at  -carbon sterically retards the backside attack of nucleophile on that carbon and
directs the incoming nucleophile to  -hydrogen.  The E2 reactivity of various alkyl halides follows the
order 30 > 20 > 10
E1 Vs E2
E1 E2
Weak Base Strong Base
30 > 20 > 10 30 > 20 > 10
Polar protic solvents Nonpolar or weakly polar (aprotic) solvents
Better leaving group required Better leaving group required
Saytzseff’s rule Saytseff’s rule
Elimination Vs Substitution Reaction
1. Bulkness of the nucleophile
More bulky nucleophiles gives elimination reaction whereas less bulky nucleophiles gives substitution
reaction

CH3
H CH2
CH3 C O + CH  X
X   CH2=CH–CH3
CH3
CH3
(more bulky)

CH3
OH + CH X 
CH3
X
CH3   HO CH
(less bulky) CH3
2. Basicity of the nucleophile
Strong bases gives elimination reaction whereas weak bases gives substitution reaction

H CH2
CH3 O + CH X 
 X
 CH2=CH–CH3
CH3
(strong base)

O
O
CH 3
C O + CH
X
X 

 CH3 C O CH CH3
CH 3
CH 3
(Weak base) CH3

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 Brilliant STUDY CENTRE LONG TERM - (IIT/AIIMS)-Chemistry
3.Temperature
Elimination reaction involves cleavage of large number of bonds. It requires high activation energy.
Therefore high temperature favour elimination reaction.

E1cb Mechanism (Elimination Conjugate Base Mechanism)

In E1 reaction, the leaving group leaves first and then the  -hydrogen. In E2 reaction both are eliminated
simultaneously. There is another possibility the H+ ions leaves first and then the leaving group. That is
the reaction proceeds through a carbanion intermediate (conjugate base)

Conditions for E1cb mechanism

1. Presence of poor leaving group

2. Presence of strongly acidic hydrogen

H F F


H


C
F
F   Cl C C F
Cl C C F  Cl C slow

Cl F Cl F
Cl F
 - Elimination Reaction
The loss of two atoms or groups occurs from    positions


 
Zn(dust ) + ZnCl2 (Freund reaction)
 
Cl + Zn+Cl
Rearrangement reaction
This type of reactions involve the migration of an atom or a group from one atom to other.
CH3

H
Eg (1) : CH3 C CH2 OH  CH3 C CH CH3

CH3 CH3

Mechanism

CH3 H
CH3
H2O H+
C OH + H +   CH3 C CH2 
 CH3 C CH CH3
CH3 CH2
CH3 CH3
CH3 CH3 C CH CH3

CH3

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 Brilliant STUDY CENTRE LONG TERM - (IIT/AIIMS)-Chemistry

CH3

CH3 CH CH 3
CH3

AlCl3
Eg (2) : + CH3 CH CH2 Cl  

Mechanism

H H

i.  AlCl C CH3
CH3 C CH2 Cl + AlCl3 
4
CH3 C CH2 
 CH3

CH3 CH3 CH3

CH3

CH3 C CH3

ii. + CH3 C CH3 

 H

CH3

CH2 OH CH3


Eg(3) : H


Mechanism H CH+
2 CH3 CH3
CH2 OH
H

 H2O
 
  H
+ H 

+H
(10)
(30)
OH

Eg (4) : + H+ 


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Brilliant STUDY CENTRE LONG TERM - (IIT/AIIMS)-Chemistry

CH3
Mechanism
OH
CH3 CH3 CH3

CH3 + H+   CH3 30 CH3

 H2O
CH3 H
20
CH3 = CH3

30 H+
more stable
CH3
CH3

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